Catalyst systems, method for preparing and using same in a polymerization process

ABSTRACT

A polymerization catalyst system and process, which utilizes a Group 14 and Group 16 containing non-crystalline compound to solubilize or emulsify polymerization catalyst components, is disclosed.

RELATED APPLICATION DATA

The present application is a divisional of U.S. patent application Ser.No. 09/714,371, filed Nov. 16, 2000, now issued as U.S. Pat. No.6,552,137.

This application is a divisional of application Ser. No. 09/458,399,filed Dec. 10, 1999 Now U.S Pat. No. 6,541,412.

FIELD OF THE INVENTION

The present invention relates to catalyst systems and to catalyst systemcomponents solubilized or emulsified in a Group 14 and Group 16containing oil or amorphous solid, and to their use in polymerizationprocesses. In a particular, preferred embodiment, the invention isdirected to catalyst systems and components solubilized or emulsifiedwith one or more siloxanes and to methods for preparing and using thesame.

BACKGROUND OF THE INVENTION

Developments in polymerization technology have provided more efficient,highly productive and economically enhanced catalyst systems andprocesses. Especially illustrative of these advances is the developmentof bulky ligand metallocene-type catalysts and of Group 15 metalcontaining catalysts. To utilize these systems in industrial slurry orgas phases processes, it is useful that they be immobilized on a carrieror support such as, for example silica or alumina. Bulky ligandmetallocene-type catalysts, however, typically exhibit lower activitywhen supported than in the corresponding homogeneous or non-supportedcatalyst systems. This “support effect” is especially dramatic when thecatalyst system utilizes a stoichiometric activator, for example a bulkyligand metallocene-type/non-coordinating anion catalyst system.

In a typical method to prepare a supported catalyst system, the catalystand activator are combined in a suitable solvent then added to thesupport or carrier material. However, systems utilizing stoichiometricactivators are often difficult to dissolve in hydrocarbon solvents andas a result are difficult to combine with a support material. Thus,there is a need to improve the solubility of catalyst compounds,especially those utilizing stoichiometric activators, to facilitate thepreparation of supported catalysts, and also to reduce the “supporteffect” when using such catalyst systems.

U.S. Pat. No. 5,747,404 discloses a polysiloxane supported metallocenecatalyst where the metallocene-type organometallic catalyst is directlybonded to a silicon atom in a siloxane polymeric oil.

PCT WO 99/14269 discloses organopolysiloxane microgel particles, havinga diameter of 5 to 200 nm, with organo-aluminum compounds immobilizedthereon, which may be used as cocatalyst with metal compounds of the IV,V, VI and VIII sub-groups of the periodic table, for oligomerizationcyclization or polymerization of olefins.

While these catalyst systems and methods have been described in the art,a need exists for an improved catalyst system and method for preparingit.

SUMMARY OF THE INVENTION

This invention provides a new and improved catalyst system, whichinclude a polymerization catalyst combined with a Group 14 and Group 16atom containing oil or amorphous solid. Preferably, the oil or amorphoussolid contains alternating atoms of silicon or germanium and oxygen andmost preferably, the oil or amorphous solid is a siloxane.

In another embodiment, the invention is directed to a catalyst systemincluding a polymerization catalyst and an activator, or an activatedpolymerization catalyst, combined with a Group 14 and Group 16 atomcontaining oil or amorphous solid.

In another embodiment the invention relates to a catalyst systemincluding a polymerization catalysts and a stoichiometric activatorcombined with a Group 14 and Group 16 atom containing oil or amorphoussolid, where preferably, the oil or amorphous solid contains alternatingatoms of silicon or germanium and oxygen.

In another aspect, the invention is directed to a catalyst system whichincludes a polymerization catalyst and activator combined with apolysiloxane microgel.

In another aspect the invention relates to a method for making acatalyst system which includes solubilizing or emulsifying apolymerization catalyst and/or an activator in one or more Group 14 andGroup 16 atom containing oil(s) or amorphous solid(s). Optionally, themethod includes further solubilizing the solution or emulsion in ahydrocarbon solvent then combining the resulting solution with a supportor carrier.

In another aspect, the invention is directed to a polymerization processutilizing a catalyst system of the invention.

In another aspect, the invention is directed to pre-polymerizationprocess utilizing a catalyst system of the invention.

DETAILED DESCRIPTION OF THE INVENTION

Introduction

The invention is directed toward a polymerization catalyst system, whichincludes a polymerization catalyst combined with a Group 14 and Group 16atom containing oil or amorphous solid. Preferably, the oil or amorphoussolid includes alternating atoms of silicon or germanium, and oxygen.Most preferably, the oil or amorphous solid is a siloxane or apolysiloxane, including microgels. The Group 14 and Group 16 atomcontaining oil or amorphous solid is used to solublize or emulsify thepolymerization catalyst and/or the catalyst activator. It has beensurprisingly discovered that these catalyst solutions or emulsions arehighly active especially when a stoichiometric activator is utilized.The polymerization catalyst systems of the invention may be used insolution, slurry, high pressure or gas phase polymerization processes.

Polymerization Catalyst

Bulky Ligand Metallocene-Type Catalyst Compounds

The Group 14 and Group 16 atom containing oil or amorphous solid may beused to create solutions or emulsions of the bulky ligandmetallocene-type polymerization catalysts described below. Generally,these catalyst compounds include half and full sandwich compounds havingone or more bulky ligands bonded to at least one metal atom. Typicalbulky ligand metallocene-type compounds are described as containing oneor more bulky ligand(s) and one or more leaving group(s) bonded to atleast one metal atom. In one preferred embodiment, at least one bulkyligands is η-bonded to the metal atom, most preferably η⁵-bonded to atransition metal atom.

The bulky ligands are generally represented by one or more open,acyclic, or fused ring(s) or ring system(s) or a combination thereof.The ring(s) or ring system(s) of these bulky ligands are typicallycomposed of atoms selected from Groups 13 to 16 atoms of the PeriodicTable of Elements. Preferably the atoms are selected from the groupconsisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorous,germanium, boron and aluminum or a combination thereof. Most preferablythe ring(s) or ring system(s) are composed of carbon atoms such as butnot limited to those cyclopentadienyl ligands or cyclopentadienyl-typeligand structures or other similar functioning ligand structure such asa pentadiene, a cyclooctatetraendiyl or an imide ligand. The metal atomis preferably selected from Groups 3 through 15 and the lanthanide oractinide series of the Periodic Table of Elements. Preferably the metalis a transition metal from Groups 4 through 12, more preferably Groups4, 5 and 6, and most preferably the transition metal is from Group 4.

In one embodiment, the Group 14 and Group 16 atom containingnon-crystalline compound may be used to create solutions or emulsions ofthe bulky ligand metallocene-type catalyst compounds represented by theformula:

L^(A)L^(B)MQ_(n)  (I)

where M is a metal atom from the Periodic Table of the Elements and maybe a Group 3 to 12 metal or from the lanthanide or actinide series ofthe Periodic Table of Elements, preferably M is a Group 4, 5 or 6transition metal, more preferably M is zirconium, hafnium or titanium.The bulky ligands, L^(A) and L^(B), are open, acyclic or fused ring(s)or ring system(s) and are any ancillary ligand system, includingunsubstituted or substituted, cyclopentadienyl ligands orcyclopentadienyl-type ligands, heteroatom substituted and/or heteroatomcontaining cyclopentadienyl-type ligands. Non-limiting examples of bulkyligands include cyclopentadienyl ligands, cyclopentaphenanthreneylligands, indenyl ligands, benzindenyl ligands, fluorenyl ligands,octahydrofluorenyl ligands, cyclooctatetraendiyl ligands,cyclopentacyclododecene ligands, azenyl ligands, azulene ligands,pentalene ligands, phosphoyl ligands, phosphinimine (WO 99/40125),pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands, borabenzeneligands and the like, including hydrogenated versions thereof, forexample tetrahydroindenyl ligands. In one embodiment, L^(A) and L^(B)may be any other ligand structure capable of η-bonding to M, preferablyη³-bonding to M and most preferably η⁵-bonding. In yet anotherembodiment, the atomic molecular weight (MW) of L^(A) or L^(B) exceeds60 a.m.u., preferably greater than 65 a.m.u. In another embodiment,L^(A) and L^(B) may comprise one or more heteroatoms, for example,nitrogen, silicon, boron, germanium, sulfur and phosphorous, incombination with carbon atoms to form an open, acyclic, or preferably afused, ring or ring system, for example, a hetero-cyclopentadienylancillary ligand. Other L^(A) and L^(B) bulky ligands include but arenot limited to bulky amides, phosphides, alkoxides, aryloxides, imides,carbolides, borollides, porphyrins, phthalocyanines, corrins and otherpolyazomacrocycles. Independently, each L^(A) and L^(B) may be the sameor different type of bulky ligand that is bonded to M. In one embodimentof formula (I) only one of either L^(A) or L^(B) is present.

Independently, each L^(A) and L^(B) may be unsubstituted or substitutedwith a combination of substituent groups R. Non-limiting examples ofsubstituent groups R include one or more from the group selected fromhydrogen, or linear, branched alkyl radicals, or alkenyl radicals,alkynyl radicals, cycloalkyl radicals or aryl radicals, acyl radicals,aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals,dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonylradicals, carbomoyl radicals, alkyl- or dialkyl-carbamoyl radicals,acyloxy radicals, acylamino radicals, aroylamino radicals, straight,branched or cyclic, alkylene radicals, or combination thereof. In apreferred embodiment, substituent groups R have up to 50 non-hydrogenatoms, preferably from 1 to 30 carbon, that can also be substituted withhalogens or heteroatoms or the like. Non-limiting examples of alkylsubstituents R include methyl, ethyl, propyl, butyl, pentyl, hexyl,cyclopentyl, cyclohexyl, benzyl or phenyl groups and the like, includingall their isomers, for example tertiary butyl, isopropyl, and the like.Other hydrocarbyl radicals include fluoromethyl, fluroethyl,difluroethyl, iodopropyl, bromobexyl, chlorobenzyl and hydrocarbylsubstituted organometalloid radicals including trimethylsilyl,trimethylgermyl, methyldiethylsilyl and the like; andhalocarbyl-substituted organometalloid radicals includingtris(trifluoromethyl)-silyl, methyl-bis(difluoromethyl)silyl,bromomethyldimethylgermyl and the like; and disubstitiuted boronradicals including dimethylboron for example; and disubstitutedpnictogen radicals including dimethylamine, dimethylphosphine,diphenylamine, methylphenylphosphine, chalcogen radicals includingmethoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide.Non-hydrogen substituents R include the atoms carbon, silicon, boron,aluminum, nitrogen, phosphorous, oxygen, tin, sulfur, germanium and thelike, including olefins such as but not limited to olefinicallyunsaturated substituents including vinyl-terminated ligands, for examplebut-3-enyl, prop-2-enyl, hex-5-enyl and the like. Also, at least two Rgroups, preferably two adjacent R groups, are joined to form a ringstructure having from 3 to 30 atoms selected from carbon, nitrogen,oxygen, phosphorous, silicon, germanium, aluminum, boron or acombination thereof. Also, a substituent group R group such as 1-butanylmay form a carbon sigma bond to the metal M.

Other ligands may be bonded to the metal M, such as at least one leavinggroup Q. For the purposes of this patent specification and appendedclaims the term “leaving group” is any ligand that can be abstractedfrom a bulky ligand metallocene-type catalyst compound to form a bulkyligand metallocene-type catalyst cation capable of polymerizing one ormore olefin(s). In one embodiment, Q is a monoanionic labile ligandhaving a sigma-bond to M. Depending on the oxidation state of the metal,the value for n is 0, 1 or 2 such that formula (I) above represents aneutral bulky ligand metallocene-type catalyst compound.

Non-limiting examples of Q ligands include weak bases such as amines,phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals havingfrom 1 to 20 carbon atoms, hydrides or halogens and the like or acombination thereof. In another embodiment, two or more Q's form a partof a fused ring or ring system. Other examples of Q ligands includethose substituents for R as described above and including cyclobutyl,cyclohexyl, heptyl, tolyl, trifluromethyl, tetramethylene,pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy,bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and thelike.

In another embodiment, the Group 14 and Group 16 atom containingnon-crystalline compound may be used to create solutions or emulsions ofthe bulky ligand metallocene-type catalyst compounds of formula (I)where L^(A) and L^(B) are bridged to each other by at least one bridginggroup, A, as represented in the following formula:

L^(A)AL^(B)MQ_(n)  (II)

These bridged compounds represented by formula (II) are known asbridged, bulky ligand metallocene-type catalyst compounds. L^(A), L^(B),M, Q and n are as defined above. Non-limiting examples of bridging groupA include bridging groups containing at least one Group 13 to 16 atom,often referred to as a divalent moiety such as but not limited to atleast one of a carbon, oxygen, nitrogen, silicon, aluminum, boron,germanium and tin atom or a combination thereof. Preferably bridginggroup A contains a carbon, silicon or germanium atom, most preferably Acontains at least one silicon atom or at least one carbon atom. Thebridging group A may also contain substituent groups R as defined aboveincluding halogens and iron. Non-limiting examples of bridging group Amay be represented by R′₂C, R′₂Si, R′₂Si R′₂Si, R′₂Ge, R′P, where R′ isindependently, a radical group which is hydride, hydrocarbyl,substituted hydrocarbyl, halocarbyl, substituted halocarbyl,hydrocarbyl-substituted organometalloid, halocarbyl-substitutedorganometalloid, disubstituted boron, disubstituted pnictogen,substituted chalcogen, or halogen or two or more R′ may be joined toform a ring or ring system. In one embodiment, the bridged, bulky ligandmetallocene-type catalyst compounds of formula (II) have two or morebridging groups A (EP 664 301 B1).

In one embodiment, the bulky ligand metallocene-type catalyst compoundsare those where the R substituents on the bulky ligands L^(A) and L^(B)of formulas (I) and (II) are substituted with the same or differentnumber of substituents on each of the bulky ligands. In anotherembodiment, the bulky ligands L^(A) and L_(B)of formulas (I) and (II)are different from each other.

Other bulky ligand metallocene-type catalyst compounds and catalystsystems useful in the invention may include those described in U.S. Pat.Nos. 5,064,802, 5,145,819, 5,149,819, 5,243,001, 5,239,022, 5,276,208,5,296,434, 5,321,106, 5,329,031, 5,304,614, 5,677,401, 5,723,398,5,753,578, 5,854,363, 5,856,547 5,858,903, 5,859,158, 5,900,517 and5,939,503 and PCT publications WO 93/08221, WO 93/08199, WO 95/07140, WO98/11144, WO 98/41530, WO 98/41529, WO 98/46650, WO 99/02540 and WO99/14221 and European publications EP-A-0 578 838, EP-A-0 638 595,EP-B-0 513 380, EP-A1-0 816 372, EP-A2-0 839 834, EP-B1-0 632 819,EP-B1-0 748 821 and EP-B1-0 757 996, all of which are herein fullyincorporated by reference.

In one embodiment, bulky ligand metallocene-type catalysts compoundsuseful in the invention include bridged heteroatom, mono-bulky ligandmetallocene-type compounds. These types of catalysts and catalystsystems are described in, for example, PCT publication WO 92/00333, WO94/07928, WO 91/04257, WO 94/03506, WO96/00244, WO 97/15602 and WO99/20637 and U.S. Pat. Nos. 5,057,475, 5,096,867, 5,055,438, 5,198,401,5,227,440 and 5,264,405 and European publication EP-A-0 420 436, all ofwhich are herein fully incorporated by reference.

In this embodiment, the bulky ligand metallocene-type catalyst compoundis represented by the formula:

L^(C)AJMQ_(n)  (III)

where M is a Group 3 to 16 metal atom or a metal selected from the Groupof actinides and lanthanides of the Periodic Table of Elements,preferably M is a Group 4 to 12 transition metal, and more preferably Mis a Group 4, 5 or 6 transition metal, and most preferably M is a Group4 transition metal in any oxidation state, especially titanium; L^(C) isa substituted or unsubstituted bulky ligand bonded to M; J is bonded toM; A is bonded to M and J; J is a heteroatom ancillary ligand; and A isa bridging group; Q is a univalent anionic ligand; and n is the integer0,1 or 2. In formula (III) above, L^(C), A and J form a fused ringsystem. In an embodiment, L^(C) of formula (III) is as defined above forL^(A), A, M and Q of formula (III) are as defined above in formula (I).

In formula (III) J is a heteroatom containing ligand in which J is anelement with a coordination number of three from Group 15 or an elementwith a coordination number of two from Group 16 of the Periodic Table ofElements. Preferably J contains a nitrogen, phosphorus, oxygen or sulfuratom with nitrogen being most preferred.

In another embodiment, the bulky ligand type metallocene-type catalystcompound is a complex of a metal, preferably a transition metal, a bulkyligand, preferably a substituted or unsubstituted pi-bonded ligand, andone or more heteroallyl moieties, such as those described in U.S. Pat.Nos. 5,527,752 and 5,747,406 and EP-B1-0 735 057, all of which areherein fully incorporated by reference.

In an embodiment, the Group 14 and Group 16 atom containingnon-crystalline compound may be used to create solutions or emulsions ofthe bulky ligand metallocene-type catalyst compounds represented by theformula:

L^(D)MQ₂(YZ)X_(n)  (IV)

where M is a Group 3 to 16 metal, preferably a Group 4 to 12 transitionmetal, and most preferably a Group 4, 5 or 6 transition metal; L^(D) isa bulky ligand that is bonded to M; each Q is independently bonded to Mand Q₂(YZ) forms a unicharged polydentate ligand; A or Q is a univalentanionic ligand also bonded to M; X is a univalent anionic group when nis 2 or X is a divalent anionic group when n is 1; n is 1 or 2.

In formula (IV), L and M are as defined above for formula (I). Q is asdefined above for formula (I), preferably Q is selected from the groupconsisting of —O—, —NR—, —CR₂— and —S—; Y is either C or S; Z isselected from the group consisting of —OR, —NR₂, —CR₃, —SR, —SiR₃, —PR₂,—H, and substituted or unsubstituted aryl groups, with the proviso thatwhen Q is —NR— then Z is selected from one of the group consisting of—OR, —NR₂, —SR, —SiR₃, —PR₂ and —H; R is selected from a groupcontaining carbon, silicon, nitrogen, oxygen, and/or phosphorus,preferably where R is a hydrocarbon group containing from 1 to 20 carbonatoms, most preferably an alkyl, cycloalkyl, or an aryl group; n is aninteger from 1 to 4, preferably 1 or 2; X is a univalent anionic groupwhen n is 2 or X is a divalent anionic group when n is 1; preferably Xis a carbamate, carboxylate, or other heteroallyl moiety described bythe Q, Y and Z combination.

In another embodiment of the invention, the bulky ligandmetallocene-type catalyst compounds are heterocyclic ligand complexeswhere the bulky ligands, the ring(s) or ring system(s), include one ormore heteroatoms or a combination thereof. Non-limiting examples ofheteroatoms include a Group 13 to 16 element, preferably nitrogen,boron, sulfur, oxygen, aluminum, silicon, phosphorous and tin. Examplesof these bulky ligand metallocene-type catalyst compounds are describedin WO 96/33202, WO 96/34021, WO 97/17379 and WO 98/22486 and EP-A1-0 874005 and U.S. Pat. Nos. 5,637,660, 5,539,124, 5,554,775, 5,756,611,5,233,049, 5,744,417, and 5,856,258 all of which are herein incorporatedby reference.

In another embodiment, the bulky ligand metallocene-type catalystcompounds are those complexes known as transition metal catalysts basedon bidentate ligands containing pyridine or quinoline moieties, such asthose described in U.S. application Ser. No. 09/103,620 filed Jun. 23,1998, which is herein incorporated by reference. In another embodiment,the bulky ligand metallocene-type catalyst compounds are those describedin PCT publications WO 99/01481 and WO 98/42664, which are fullyincorporated herein by reference.

In one embodiment, the Group 14 and Group 16 atom containingnon-crystalline compound may be used to create solutions or emulsions ofthe bulky ligand metallocene-type catalyst compounds represented by theformula:

((Z)XA_(t)(YJ))_(q)MQ_(n)  (V)

where M is a metal selected from Group 3 to 13 or lanthanide andactinide series of the Periodic Table of Elements; Q is bonded to M andeach Q is a monovalent, bivalent, or trivalent anion; X and Y are bondedto M; one or more of X and Y are heteroatoms, preferably both X and Yare heteroatoms; Y is contained in a heterocyclic ring J, where Jcomprises from 2 to 50 non-hydrogen atoms, preferably 2 to 30 carbonatoms; Z is bonded to X, where Z comprises 1 to 50 non-hydrogen atoms,preferably 1 to 50 carbon atoms, preferably Z is a cyclic groupcontaining 3 to 50 atoms, preferably 3 to 30 carbon atoms; t is 0 or 1;when t is 1, A is a bridging group joined to at least one of X,Y or J,preferably X and J; q is 1 or 2; n is an integer from 1 to 4 dependingon the oxidation state of M. In one embodiment, where X is oxygen orsulfur then Z is optional. In another embodiment, where X is nitrogen orphosphorous then Z is present. In an embodiment, Z is preferably an arylgroup, more preferably a substituted aryl group.

It is also within the scope of this invention, in one embodiment, thatthe bulky ligand metallocene-type catalyst compounds include complexesof Ni²⁺ and Pd²⁺ described in the articles Johnson, et al., “New Pd(II)-and Ni(II)-Based Catalysts for Polymerization of Ethylene anda-Olefins”, J. Am. Chem. Soc. 1995, 117, 6414-6415 and Johnson, et al.,“Copolymerization of Ethylene and Propylene with Functionalized VinylMonomers by Palladium(II) Catalysts”, J. Am. Chem. Soc., 1996, 118,267-268, and WO 96/23010 published Aug. 1, 1996, WO 99/02472, U.S. Pat.Nos. 5,852,145, 5,866,663 and 5,880,241, which are all herein fullyincorporated by reference. These complexes can be either dialkyl etheradducts, or alkylated reaction products of the described dihalidecomplexes that can be activated to a cationic state by the activators ofthis invention described below.

Also included as bulky ligand metallocene-type catalyst are thosediimine based ligands of Group 8 to 10 metal compounds disclosed in PCTpublications WO 96/23010 and WO 97/48735 and Gibson, et. al., Chem.Comm., pp. 849-850 (1998), all of which are herein incorporated byreference.

Other bulky ligand metallocene-type catalysts are those Group 5 and 6metal imido complexes described in EP-A2-0 816 384 and U.S. Pat. No.5,851,945, which is incorporated herein by reference. In addition, bulkyligand metallocene-type catalysts include bridged bis(arylamido) Group 4compounds described by D. H. McConville, et al., in Organometallics1195, 14, 5478-5480, which is herein incorporated by reference. Inaddition, bridged bis(amido) catalyst compounds are described in WO96/27439, which is herein incorporated by reference. Other bulky ligandmetallocene-type catalysts are described as bis(hydroxy aromaticnitrogen ligands) in U.S. Pat. No. 5,852,146, which is incorporatedherein by reference. Other metallocene-type catalysts containing one ormore Group 15 atoms include those described in WO 98/46651, which isherein incorporated herein by reference. Still another metallocene-typebulky ligand metallocene-type catalysts include those multinuclear bulkyligand metallocene-type catalysts as described in WO 99/20665, which isincorporated herein by reference.

It is also contemplated that in one embodiment, the bulky ligandmetallocene-type catalysts of the invention described above includetheir structural or optical or enantiomeric isomers (meso and racemicisomers, for example see U.S. Pat. No. 5,852,143, incorporated herein byreference) and mixtures thereof.

Group 15 Containing Polymerization Catalyst

The Group 14 and Group 16 atom containing oil or amorphous solid mayalso be used to create solutions or emulsions of Group 15 metalcontaining polymerization catalyst. Generally, these catalysts includesa Group 3 to 14 metal atom, preferably a Group 3 to 7, more preferably aGroup 4 to 6, and even more preferably a Group 4 metal atom, bound to atleast one leaving group and also bound to at least two Group 15 atoms,at least one of which is also bound to a Group 15 or 16 atom throughanother group.

Preferably, at least one of the Group 15 atoms is also bound to a Group15 or 16 atom through another group which may be a C₁ to C₂₀ hydrocarbongroup, a heteroatom containing group, silicon, germanium, tin, lead, orphosphorus, wherein the Group 15 or 16 atom may also be bound to nothingor a hydrogen, a Group 14 atom containing group, a halogen, or aheteroatom containing group, and wherein each of the two Group 15 atomsare also bound to a cyclic group and may optionally be bound tohydrogen, a halogen, a heteroatom or a hydrocarbyl group, or aheteroatom containing group.

It is also contemplated that any one of the catalyst compounds describedabove may have at least one fluoride or fluorine containing leavinggroup as described in U.S. application Ser. No. 09/191,916 filed Nov.13, 1998.

In another embodiment of the invention the composition containingalternating atoms of Group 14 and Group 16 may be used to createsolutions or emulsions including one or more bulky ligandmetallocene-type catalyst compounds, and one or more conventional-typecatalyst compounds or catalyst systems. Non-limiting examples of mixedcatalysts and catalyst systems are described in U.S. Pat. Nos.4,159,965, 4,325,837, 4,701,432, 5,124,418, 5,077,255, 5,183,867,5,391,660, 5,395,810, 5,691,264, 5,723,399 and 5,767,031 and PCTPublication WO 96/23010 published Aug. 1, 1996, all of which are hereinfully incorporated by reference.

Activator Compositions

The above described polymerization catalyst compounds are typicallyactivated in various ways to yield compounds having a vacantcoordination site that will coordinate, insert, and polymerizeolefin(s). The catalyst system of the invention may include an activatoror activators combined with the composition containing alternating atomsof Group 14 and Group 16.

For the purposes of this patent specification and appended claims, theterm “activator” is defined to be any compound or component or methodwhich can activate any of the bulky ligand metallocene-type catalystcompounds and/or the Group 15 metal containing catalysts describedabove. Non-limiting activators, for example, may include a Lewis acid ora non-coordinating ionic activator or ionizing activator or any othercompound including Lewis bases, aluminum alkyls, conventional-typecocatalysts and combinations thereof that can convert a neutral bulkyligand metallocene-type catalyst compound or Group 15 containing metalcompound to a catalytically active bulky ligand metallocene-type orGroup 15 containing metal compound catalyst cation.

It is within the scope of this invention to use as alumoxane or modifiedalumoxanes as an activator. There are a variety of methods for preparingalumoxane and modified alumoxanes, non-limiting examples of which aredescribed in U.S. Pat. Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199,5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815,5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793,5,391,529, 5,693,838, 5,731,253, 5,731,451, 5,744,656, 5,847,177,5,854,166, 5,856,256 and 5,939,346 and European publications EP-A-0 561476, EP-B1-0 279 586, EP-A-0 594-218 and EP-B1-0 586 665, and PCTpublication WO 94/10180, all of which are herein fully incorporated byreference.

In one embodiment aluminoxanes or modified alumoxanes are combined withcatalyst compound(s) solubilized or emulsified in the compositioncontaining alternating atoms of Group 14 and Group 16 of the invention.In another embodiment MMAO3A (modified methyl alumoxane in heptane,commercially available from Akzo Chemicals, Inc., Holland, under thetrade name Modified Methylalumoxane type 3A, see for example thosealuminoxanes disclosed in U.S. Pat. No. 5,041,584, which is hereinincorporated by reference) is combined with the catalyst compound(s) andthe composition containing alternating atoms of Group 14 and Group 16,to form a catalyst system of the invention.

Organoaluminum compounds useful as activators include trimethylaluminum,triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum and the like.

It is within the scope of this invention to use an ionizing orstoichiometric activator, neutral or ionic, such as tri (n-butyl)ammonium tetrakis (pentafluorophenyl) boron, a trisperfluorophenyl boronmetalloid precursor or a trisperfluoronaphtyl boron metalloid precursor,polyhalogenated heteroborane anions (WO 98/43983) or combinationthereof, that would ionize the neutral bulky ligand metallocene-typecatalyst and/or the Group 15 containing metal compound. It is alsowithin the scope of this invention to use neutral or ionic activatorsalone or in combination with alumoxane or modified alumoxane activators.

An example of a neutral stoichiometric activator, which may besolubilized or emulsified by the composition containing alternatingatoms of Group 14 and Group 16, include tri-substituted boron,tellurium, aluminum, gallium and indium or mixtures thereof. The threesubstituent groups are each independently selected from alkyls,alkenyls, halogen, substituted alkyls, aryls arylhalides, alkoxy andhalides. Preferably, the three groups are independently selected fromhalogen, mono or multicyclic (including halosubstituted) aryls, alkyls,and alkenyl compounds and mixtures thereof, preferred are alkenyl groupshaving 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms,alkoxy groups having 1 to 20 carbon atoms and aryl groups having 3 to 20carbon atoms (including substituted aryls). More preferably, the threegroups are alkyls having 1 to 4 carbon groups, phenyl, napthyl ormixtures thereof. Most preferably, the neutral stoichiometric activatoris trisperfluorophenyl boron or trisperfluoronapthyl boron.

In a preferred embodiment, the catalyst system of the invention includesan ionic stoichiometric activator solubilized or emulsified by thecomposition containing alternating atoms of Group 14 and Group 16.Ionizing activator compounds may contain an active proton, or some othercation associated with but not coordinated to or only looselycoordinated to the remaining ion of the ionizing compound. Suchcompounds and the like are described in European publications EP-A-0 570982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 andEP-A-0 277 004, and U.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741,5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. patentapplication Ser. No. 08/285,380, filed Aug. 3, 1994, all of which areherein fully incorporated by reference.

In a preferred embodiment, the stoichiometric activators include acation and an anion component, and may be represented by the followingformula:

(L-H)_(d) ⁺(A^(d−))  (VI)

wherein L′ is an neutral Lewis base;

H is hydrogen;

(L-H)⁺ is a Bronsted acid

A^(d−) is a non-coordinating anion having the charge d−

d is an integer from 1 to 3.

The cation component, (L-H)_(d) ⁺ may include Bronsted acids such asprotons or protonated Lewis bases or reducible Lewis acids capable ofprotonating or abstracting a moiety, such as an akyl or aryl, from thebulky ligand metallocene-type or Group 15 containing transition metalcatalyst precursor, resulting in a cationic transition metal species.

The activating cation (L-H)_(d) ⁺ may be a Bronsted acid, capable ofdonating a proton to the transition metal catalytic precursor resultingin a transition metal cation, including ammoniums, oxoniums,phosphoniums, silyliums and mixtures thereof, preferably ammoniums ofmethylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline,methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline,p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine,triphenylphosphine, and diphenylphosphine, oxomiuns from ethers such asdimethyl ether diethyl ether, tetrahydrofuran and dioxane, sulfoniumsfrom thioethers, such as diethyl thioethers and tetrahydrothiophene andmixtures thereof. Most preferably, dimethylanaline. The activatingcation (L-H)_(d) ⁺ may also be an abstracting moiety such as silver,carboniums, tropylium, carbeniums, ferroceniums and mixtures, preferablycarboniums and ferroceniums. Most preferably (L-H)_(d) ⁺ is triphenylcarbonium.

The anion component A^(d−) include those having the formula[M^(k+)Q_(n)]^(d−) wherein k is an integer from 1 to 3; n is an integerfrom 2-6; n−k=d; M is an element selected from Group 13 of the PeriodicTable of the Elements and Q is independently a hydride, bridged orunbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl,substituted hydrocarbyl, halocarbyl, substituted halocarbyl, andhalosubstituted-hydrocarbyl radicals, said Q having up to 20 carbonatoms with the proviso that in not more than 1 occurrence is Q a halide.Preferably, each Q is a fluorinated hydrocarbyl group having 1 to 20carbon atoms, more preferably each Q is a fluorinated aryl group, andmost preferably each Q is a pentafluoryl aryl group.

In a most preferred embodiment, the ionic stoichiometric activator(L-H)_(d) ⁺ (A^(d−)) is N,N-dimethylaniliniumtetra(perfluorophenyl)borate or triphenylcarbeniumtetra(perfluorophenyl)borate.

Examples of suitable A^(d−) also include diboron compounds as disclosedin U.S. Pat. No. 5,447,895, which is fully incorporated herein byreference.

In one embodiment, an activation method using ionizing ionic compoundsnot containing an active proton but capable of producing a Group 15containing metal compound cation or bulky ligand metallocene-typecatalyst cation and their non-coordinating anion are also contemplated,and are described in EP-A-0 426 637, EP-A-0 573 403 and U.S. Pat. No.5,387,568, which are all herein incorporated by reference.

Other activators include those described in PCT publication WO 98/07515such as tris (2, 2′, 2″-nonafluorobiphenyl) fluoroaluminate, whichpublication is fully incorporated herein by reference. Combinations ofactivators are also contemplated by the invention, for example,alumoxanes and ionizing activators in combinations, see for example,EP-B1 0 573 120, PCT publications WO 94/07928 and WO 95/14044 and U.S.Pat. Nos. 5,153,157 and 5,453,410 all of which are herein fullyincorporated by reference.

Other suitable activators are disclosed in WO 98/09996, incorporatedherein by reference, which describes activating bulky ligandmetallocene-type catalyst compounds with perchlorates, periodates andiodates including their hydrates. WO 98/30602 and WO 98/30603,incorporated by reference, describe the use of lithium(2,2′-bisphenyl-ditrimethylsilicate)•4THF as an activator for a bulkyligand metallocene-type catalyst compound. WO 99/18135, incorporatedherein by reference, describes the use of organo-boron-aluminumacitivators. EP-B1-0 781 299 describes using a silylium salt incombination with a non-coordinating compatible anion. Also, methods ofactivation such as using radiation (see EP-B1-0 615 981 hereinincorporated by reference), electrochemical oxidation, and the like arealso contemplated as activating methods for the purposes of renderingthe neutral bulky ligand metallocene-type catalyst compound or precursorto a bulky ligand metallocene-type cation capable of polymerizingolefins. Other activators or methods for activating a bulky ligandmetallocene-type catalyst compound are described in for example, U.S.Pat. Nos. 5,849,852, 5,859,653 and 5,869,723 and WO 98/32775, WO99/42467 (dioctadecylmethylammonium-bis(tris(pentafluorophenyl)borane)benzimidazolide), which are herein incorporated by reference.

Group 14 and Group 16 Atom Containing Oils or Amorphous Solids

One or more Group 14 and Group 16 containing oil or amorphous solid arecombined with the above described bulky ligand metallocene-type catalystcompounds and/or Group 15 metal containing catalyst compounds and/oractivator compositions to form a catalyst, a catalyst activator, or anactivated catalyst solution or emulsion. Preferably, the oil oramorphous solid contains alternating atoms of Group 14 and Group 16.More preferably, the oil or amorphous solid contains silicon orgermanium and oxygen. More preferably the oil or amorphous solid is asiloxane, polysiloxane or a polysiloxane microgel and most preferably asiloxane. The Group 14 and Group 16 containing oil or amorphous solid,and in particular siloxanes, improve the solubility of catalyst and/oractivators to form catalyst solutions or emulsions of relative higheractivity, particularly when stoichiometric activators are utilized.

The Group 14 and Group 16 containing oil or amorphous solid areavailable in a wide range of solubility, and may be represented by oneof the general formulae appearing below:

T-M(R¹)₂-Q-(M(R²)₂-Q)_(n-)-M(R¹)₂-T  (VII)

T-M(R¹)₂-Q-(M(R²)₂-Q)_(n)-(M(R³)₂-Q)_(m)-M(R¹)₂-T  (VIII)

where each T is independently selected from, hydrogen, an alky, alkoxy,aryl, substituted aryl, cycloalkyl, substituted cyclic alkyl, cyclicaralkyl, substituted cyclic aralkyl, heteroatom, vinyl, silyl, silyloxy,vinylsiloxy, hydride, haloaryl, haloalkyl, or vinylsilyl containinggroup. Preferably, each T is independently selected from C₁ to C₂₀ alkylor an aryl group. More preferably each T is independently a methyl,ethyl, isopropyl butyl, vinyl or phenyl group, and most preferably amethyl, ethyl or vinyl group.

Each M is independently an atom of Group 14 of the Periodic Table,preferably M is silicon or germanium, more preferably M is silicon.

Each Q is independently an atom of Group 16 of the Periodic Table of theElements, preferably Q is oxygen.

Each R¹ and each R² is independently selected from hydrogen, an alkyl,alkoxy, aryl, substituted aryl, cycloalkyl, substituted cyclic alkyl,cyclic aralkyl, substituted cyclic aralkyl, heteroatom, vinyl, silyl,silyloxy, vinylsiloxy, hydride, haloaryl, haloalkyl, or vinylsilylcontaining group. Preferably, each R¹ and each R² is independentlyselected from an alkyl group having 1 to 20 carbon atoms or an arylgroup. More preferably, each R¹ and each R² is independently a methylgroup, an ethyl group, or a haloalkyl. Most preferably, each R¹ and eachR² is independently a methyl group, an ethyl group, or a fluoro-alkyl.

Each R³ is independently selected from hydrogen, an alkyl, alkoxy, aryl,substituted aryl, cycloalkyl, substituted cyclic alkyl, cyclic aralkyl,substituted cyclic aralkyl, heteroatom, vinyl, silyl, silyloxy,vinylsiloxy, hydride, haloaryl, haloalkyl, or vinylsilyl containinggroup. Preferably, each R³ is independently selected from an alkyl grouphaving 1 to 20 carbon atoms, a halogenated alkyl group, or an arylgroup. Most preferably, R³ is a halogenated or non-halogenated methyl,ethyl, propyl or phenyl group.

n and m are independently 0 or an integer from 1 to 40,000, preferablyfrom 1 to 20,000 and more preferably from 1 and 10,000.

In one embodiment, the terminal groups T, may be connected, by forexample a heteroatom or by a polysiloxy group to form a cyclic siloxane.

The alkyl group, as used above, may be a linear, branched alkylradicals, or alkenyl radicals, alkynyl radicals, cycloalkyl radicals oraryl radicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxyradicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonylradicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- ordialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals,aroylamino radicals, straight, branched or cyclic, alkylene radicals, orcombination thereof. An aralkyl group is defined to be a substitutedaryl group.

In one embodiment, the composition containing alternating atoms of Group14 and Group 16 of the invention, preferably a siloxane or combinationof siloxanes, has a viscosity of between about 1 cSt and 2,500,000 cSt,more preferably between about 100 cSt and 500,000 cSt, more preferablybetween about 100 cSt to about 50,000 cSt, and even more preferablybetween about 500 and 5000 cSt.

In one embodiment, the composition containing alternating atoms of Group14 and Group 16 of the invention, preferably a siloxane or combinationof siloxanes, has a number average molecular weight (M_(n)) of betweenabout 40 and 500,000, more preferably between about 60 and 100,000 andeven more preferably between about 1,000 and 60,000 and most preferablybetween about 5,000 and 40,000.

In a most preferred embodiment, the composition containing alternatingatoms of Group 14 and Group 16 is a vinyl terminated dimethylmethyltrifluoropropylsiloxane with a M_(n) of between about 20,000 andabout 40,000.

Preparation of the Catalyst Solution or Emulsion

The method for making the catalyst solution or emulsion of the inventiongenerally involves the combining, contacting, blending one or more ofthe Group 14 and Group 16 containing oil or amorphous solid describedabove with any catalyst compounds and/or activator compounds, alone orin combinations. Preferably, the Group 14 and Group 16 containing oil oramorphous solid is first purified as is known in the art. Mostpreferably, the Group 14 and Group 16 containing oil or amorphous solidis a siloxane, or combination of siloxanes, which has been purified, forexample, by vacuum drying and/or refluxing in a suitable solvent, forexample toluene, as is known in the art.

In a preferred embodiment, the catalyst solution or emulsion of theinvention is formed by first combining the catalyst compound and/or theactivator composition with an aliphatic or aromatic hydrocarbon, mostpreferably toluene, and then combining with the Group 14 and Group 16containing oil or amorphous solid. When a siloxane is utilized, theresulting solution or emulsion is typically yellow or orange in color.

Optionally, a scavenger, preferably tri-n-octylaluminum, is added toGroup 14 and Group 16 containing oil or amorphous solid, preferablyprior to the addition of the catalyst compound. While not limited to anyone particular theory, it is believed that the addition of a scavengeroperates to remove residual hydroxyl groups and water from the preferredsiloxane.

In general the catalyst compound(s) and the activator are combined inthe solution or emulsion in mole ratios of catalyst compound toactivator of about 1000:1 to about 0.5:1. In a preferred embodiment thecatalyst compounds and the activator are combined in a mole ratio ofabout 300:1 to about 1:1, and preferably about 150:1 to about 1:1. Forboranes, borates, aluminates, etc. the mole ratio of catalyst toactivator is preferably about 1:1 to about 10:1 and for alkyl aluminumcompounds (such as diethylaluminum chloride combined with water) themole ratio is preferably about 0.5:1 to about 10:1. In a preferredembodiment, an ionizing activator is used and the mole ratio of themetal of the ionizing activator component to the metal of the catalystcompounds between about 0.3:1 to about 3:1.

Optionally, the catalyst solution or emulsion may be further dilutedwith aliphatic or aromatic hydrocarbon solvent, preferably pentane ortoluene.

In general, the Group 14 and Group 16 containing oil or amorphous solid,preferably a siloxane, and the catalyst compound are combined in anyuseful weight ratio of weight siloxane:weight catalyst. Preferably, theweight ratio of weight siloxane:weight catalyst is between about 1:10 to100:1 preferably between about 1:1 and about 70:1, more preferablybetween about 1:1 and about 50:1 and most preferably between about 20:1to about 40:1

In another embodiment, at least one catalyst compound, at least oneactivator, and at least one Group 14 and Group 16 containing oil oramorphous solid, as described above, are combined to form a mixture withthe mixture being heated during activation to improve homogeneity. Themixture is heated to between about 30° C. and about 250° C., morepreferably between about 40° C. and about 100° C. and even morepreferably between about 50° C. and about 70° C.

In another embodiment, the catalyst of the invention has a specificactivity of between about 1 to 100,000,000 g/mmol·atm·h, more preferablybetween about 10 and 100,000 g/mmol·atm·h, more preferably between about25 and 50,000 g/mmol·atm·h.

Supports, Carriers and General Supporting Techniques

The above described catalyst and/or activator solutions or emulsions maybe combined with one or more support materials or carriers using one ofthe support methods well known in the art or as described below to forma supported catalyst system. For example, the Group 14 and Group 16containing oil or amorphous solid catalyst and/or activator solution oremulsion may be deposited on, contacted with, vaporized with, bonded to,or incorporated within, adsorbed or absorbed in, or on, a support orcarrier.

The terms “support” or “carrier”, for purposes of this patentspecification, are used interchangeably and are any support material,preferably a porous support material, including inorganic or organicsupport materials. Non-limiting examples of inorganic support materialsinclude inorganic oxides and inorganic chlorides. Other carriers includeresinous support materials such as polystyrene, functionalized orcrosslinked organic supports, such as polystyrene divinyl benzenepolyolefins or polymeric compounds, zeolites, talc, clays, or any otherorganic or inorganic support material and the like, or mixtures thereof.

The preferred carriers are inorganic oxides that include those Group 2,3, 4, 5, 13 or 14 metal oxides. The preferred supports include silica,alumina, silica-alumina, magnesium chloride, and mixtures thereof. Otheruseful supports include magnesia, titania, zirconia, montmorillonite(EP-B1 0 511 665), phyllosilicate, and the like. Also, combinations ofthese support materials may be used, for example, silica-chromium,silica-alumina, silica-titania and the like. Additional supportmaterials may include those porous acrylic polymers described in EP 0767 184 B1, which is incorporated herein by reference.

It is preferred that the carrier, most preferably an inorganic oxide,has a surface area in the range of from about 10 to about 700 m²/g, porevolume in the range of from about 0.1 to about 4.0 cc/g and averageparticle size in the range of from about 5 to about 500 μm. Morepreferably, the surface area of the carrier is in the range of fromabout 50 to about 500 m²/g, pore volume of from about 0.5 to about 3.5cc/g and average particle size of from about 10 to about 200 μm. Mostpreferably the surface area of the carrier is in the range is from about100 to about 400 m²/g, pore volume from about 0.8 to about 3.0 cc/g andaverage particle size is from about 5 to about 100 μm. The average poresize of the carrier of the invention typically has pore size in therange of from 10 to 100 Å, preferably 50 to about 500 Å, and mostpreferably 75 to about 350 Å.

Examples of supporting bulky ligand metallocene-type catalyst systems,which may be used to support the catalyst and/or activator solutions oremulsions of the invention, are described in U.S. Pat. Nos. 4,701,432,4,808,561, 4,912,075, 4,925,821, 4,937,217, 5,008,228, 5,238,892,5,240,894, 5,332,706, 5,346,925, 5,422,325, 5,466,649, 5,466,766,5,468,702, 5,529,965, 5,554,704, 5,629,253, 5,639,835, 5,625,015,5,643,847, 5,665,665, 5,698,487, 5,714,424, 5,723,400, 5,723,402,5,731,261, 5,759,940, 5,767,032, 5,770,664, 5,846,895 and 5,939,348 andU.S. application Ser. Nos. 271,598 filed Jul. 7, 1994 and 788,736 filedJan. 23, 1997 and PCT publications WO 95/32995, WO 95/14044, WO 96/06187and WO 97/02297, and EP-B1-0 685 494 all of which are herein fullyincorporated by reference.

There are various other methods in the art for supporting thepolymerization catalyst solutions or emulsions of the invention. Forexample, the bulky ligand metallocene-type catalyst compound of theinvention may contain a polymer bound ligand as described in U.S. Pat.Nos. 5,473,202 and 5,770,755, which is herein fully incorporated byreference; the bulky ligand metallocene-type catalyst system of theinvention may be spray dried as described in U.S. Pat. No. 5,648,310,which is herein fully incorporated by reference; the support used withthe bulky ligand metallocene-type catalyst system of the invention maybe functionalized as described in European publication EP-A-0 802 203,which is herein fully incorporated by reference, or at least onesubstituent or leaving group may be selected as described in U.S. Pat.No. 5,688,880, which is herein fully incorporated by reference.

In another embodiment, an antistatic agent or surface modifier, that isused in the preparation of the supported catalyst system as described inPCT publication WO 96/11960, which is herein fully incorporated byreference, may be used with the Group 14 and Group 16 containing oil oramorphous solid catalyst and/or activator solutions or emulsions of theinvention. The catalyst systems of the invention can be prepared in thepresence of an olefin, for example hexene-1.

In another embodiment, catalyst containing emulsions or solutions of theinvention can be combined with a carboxylic acid salt of a metal ester,for example aluminum carboxylates such as aluminum mono, di- andtri-stearates, aluminum octoates, oleates and cyclohexylbutyrates, asdescribed in U.S. application Ser. No. 09/113,216, filed Jul. 10, 1998.

A preferred method for producing a supported bulky ligandmetallocene-type catalyst system, which maybe used to support thecatalyst and/or activator solutions or emulsions of the invention, isdescribed below, and is described in U.S. application Ser. Nos. 265,533,filed Jun. 24, 1994 and 265,532, filed Jun. 24, 1994 and PCTpublications WO 96/00245 and WO 96/00243 both published Jan. 4, 1996,all of which are herein fully incorporated by reference. In thispreferred method, the catalyst compound is slurried in a liquid and witha Group 14 and Group 16 containing oil or amorphous solid to form acatalyst solution or emulsion. A separate solution is formed containingan activator and a liquid. The liquid may be any compatible solvent orother liquid capable of forming a solution or the like with the catalystcompounds and/or activator. In the most preferred embodiment the liquidis a cyclic aliphatic or aromatic hydrocarbon, most preferably toluene.The catalyst compound and activator solutions are mixed together heatedand added to a heated porous support or a heated porous support is addedto the solutions such that the total volume of the bulky ligandmetallocene-type catalyst compound solution and the activator solutionor the bulky ligand metallocene-type catalyst compound and activatorsolution is less than four times the pore volume of the porous support,more preferably less than three times, even more preferably less thantwo times; preferred ranges being from 1.1 times to 3.5 times range andmost preferably in the 1.2 to 3 times range.

Procedures for measuring the total pore volume of a porous support arewell known in the art. Details of one of these procedures is discussedin Volume 1, Experimental Methods in Catalytic Research (Academic Press,1968) (specifically see pages 67-96). This preferred procedure involvesthe use of a classical BET apparatus for nitrogen absorption. Anothermethod well known in the art is described in Innes, Total Porosity andParticle Density of Fluid Catalysts By Liquid Titration, Vol. 28, No. 3,Analytical Chemistry 332-334 (March, 1956).

Polymerization Process

The Group 14 and Group 16 containing oil or amorphous solid containingcatalyst compositions or systems of the invention described above aresuitable for use in any prepolymerization and/or polymerization processover a wide range of temperatures and pressures. The temperatures may bein the range of from −60° C. to about 280° C., preferably from 50° C. toabout 200° C., and the pressures employed may be in the range from 1atmosphere to about 500 atmospheres or higher.

Polymerization processes include solution, gas phase, slurry phase and ahigh pressure process or a combination thereof. Preferred is a gas phaseor slurry phase polymerization of one or more olefins at least one ofwhich is ethylene or propylene.

In one embodiment, the process of this invention is directed toward asolution, high pressure, slurry or gas phase polymerization process ofone or more olefin monomers having from 2 to 30 carbon atoms, preferably2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms. Theinvention is particularly well suited to the polymerization of two ormore olefin monomers of ethylene, propylene, butene-1, pentene-1,4-methyl-pentene-1, hexene-1, octene-1 and decene-1.

Other monomers useful in the polymerization process of the inventioninclude ethylenically unsaturated monomers, diolefins having 4 to 18carbon atoms, conjugated or nonconjugated dienes, polyenes, vinylmonomers and cyclic olefins. Non-limiting monomers useful in theinvention may include norbornene, norbornadiene, isobutylene, isoprene,vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidenenorbornene, dicyclopentadiene and cyclopentene.

In the most preferred embodiment of the process of the invention, acopolymer of ethylene is produced, where with ethylene, a comonomerhaving at least one alpha-olefin having from 4 to 15 carbon atoms,preferably from 4 to 12 carbon atoms, and most preferably from 4 to 8carbon atoms, is polymerized in a polymerization process.

In another embodiment of the process of the invention, ethylene orpropylene is polymerized with at least two different comonomers,optionally one of which may be a diene, to form a terpolymer.

In one embodiment, the invention is directed to a polymerization processfor polymerizing propylene alone or with one or more other monomersincluding ethylene, and/or other olefins having from 4 to 12 carbonatoms. Polypropylene polymers may be produced using the particularlybridged bulky ligand metallocene-type catalysts as described in U.S.Pat. Nos. 5,296,434 and 5,278,264, both of which are herein incorporatedby reference.

Typically in a gas phase polymerization process a continuous cycle isemployed where in one part of the cycle of a reactor system, a cyclinggas stream, otherwise known as a recycle stream or fluidizing medium, isheated in the reactor by the heat of polymerization. This heat isremoved from the recycle composition in another part of the cycle by acooling system external to the reactor. Generally, in a gas fluidizedbed process for producing polymers, a gaseous stream containing one ormore monomers is continuously cycled through a fluidized bed in thepresence of a catalyst under reactive conditions. The gaseous stream iswithdrawn from the fluidized bed and recycled back into the reactor.Simultaneously, polymer product is withdrawn from the reactor and freshmonomer is added to replace the polymerized monomer. (See for exampleU.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352,749,5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661 and 5,668,228, allof which are fully incorporated herein by reference.)

The reactor pressure in a gas phase process may vary from about 100 psig(690 kPa) to about 500 psig (3448 kPa), preferably in the range of fromabout 200 psig (1379 kPa) to about 400 psig (2759 kPa), more preferablyin the range of from about 250 psig (1724 kPa) to about 350 psig (2414kPa).

The reactor temperature in a gas phase process may vary from about 30°C. to about 120° C., preferably from about 60° C. to about 115° C., morepreferably in the range of from about 70° C. to 110° C., and mostpreferably in the range of from about 70° C. to about 95° C.

Other gas phase processes contemplated by the process of the inventioninclude series or multistage polymerization processes. Also gas phaseprocesses contemplated by the invention include those described in U.S.Pat. Nos. 5,627,242, 5,665,818 and 5,677,375, and European publicationsEP-A-0 794 200 EP-B1-0 649 992, EP-A-0 802 202 and EP-B-634 421 all ofwhich are herein filly incorporated by reference.

In a preferred embodiment, the reactor utilized in the present inventionis capable and the process of the invention is producing greater than500 lbs of polymer per hour (227 Kg/hr) to about 200,000 lbs/hr (90,900Kg/hr) or higher of polymer, preferably greater than 1000 lbs/hr (455Kg/hr), more preferably greater than 10,000 lbs/hr (4540 Kg/hr), evenmore preferably greater than 25,000 lbs/hr (11,300 Kg/hr), still morepreferably greater than 35,000 lbs/hr (15,900 Kg/hr), still even morepreferably greater than 50,000 lbs/hr (22,700 Kg/hr) and most preferablygreater than 65,000 lbs/hr (29,000 Kg/hr) to greater than 100,000 lbs/hr(45,500 Kg/hr).

A slurry polymerization process generally uses pressures in the range offrom about 1 to about 50 atmospheres and even greater and temperaturesin the range of 0° C. to about 120° C. In a slurry polymerization, asuspension of solid, particulate polymer is formed in a liquidpolymerization diluent medium to which ethylene and comonomers and oftenhydrogen along with catalyst are added. The suspension including diluentis intermittently or continuously removed from the reactor where thevolatile components are separated from the polymer and recycled,optionally after a distillation, to the reactor. The liquid diluentemployed in the polymerization medium is typically an alkane having from3 to 7 carbon atoms, preferably a branched alkane. The medium employedshould be liquid under the conditions of polymerization and relativelyinert. When a propane medium is used the process must be operated abovethe reaction diluent critical temperature and pressure. Preferably, ahexane or an isobutane medium is employed.

A preferred polymerization technique of the invention is referred to asa particle form polymerization, or a slurry process where thetemperature is kept below the temperature at which the polymer goes intosolution. Such technique is well known in the art, and described in forinstance U.S. Pat. No. 3,248,179 which is fully incorporated herein byreference. Other slurry processes include those employing a loop reactorand those utilizing a plurality of stirred reactors in series, parallel,or combinations thereof. Non-limiting examples of slurry processesinclude continuous loop or stirred tank processes. Also, other examplesof slurry processes are described in U.S. Pat. No. 4,613,484, which isherein fully incorporated by reference.

In an embodiment the reactor used in the slurry process of the inventionis capable of and the process of the invention is producing greater than2000 lbs of polymer per hour (907 Kg/hr), more preferably greater than5000 lbs/hr (2268 Kg/hr), and most preferably greater than 10,000 lbs/hr(4540 Kg/hr). In another embodiment the slurry reactor used in theprocess of the invention is producing greater than 15,000 lbs of polymerper hour (6804 Kg/hr), preferably greater than 25,000 lbs/hr (11,340Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).

Examples of solution processes, where the siloxane catalyst and/oractivator solutions or emulsions of the invention may be utilized, aredescribed in U.S. Pat. Nos. 4,271,060, 5,001,205, 5,236,998 and5,589,555, which are fully incorporated herein by reference.

A preferred process of the invention is where the process is operated inthe presence of a bulky ligand metallocene-type catalyst system of theinvention and in the absence of or essentially free of any scavengers,such as triethylaluminum, trimethylaluminum, tri-isobutylaluminum andtri-n-hexylaluminum and diethyl aluminum chloride, dibutyl zinc and thelike. This preferred process is described in PCT publication WO 96/08520and U.S. Pat. No. 5,712,352 and 5,763,543, which are herein fullyincorporated by reference.

In one embodiment of the invention, olefin(s), preferably C₂ to C₃₀olefin(s) or alpha-olefin(s), preferably ethylene or propylene orcombinations thereof are prepolymerized in the presence of the catalystsolution or emulsion of the invention prior to the main polymerization.The prepolymerization can be carried out batchwise or continuously ingas, solution or slurry phase including at elevated pressures. Theprepolymerization can take place with any olefin monomer or combinationand/or in the presence of any molecular weight controlling agent such ashydrogen. For examples of prepolymerization procedures, see U.S. Pat.Nos. 4,748,221, 4,789,359, 4,923,833, 4,921,825, 5,283,278 and 5,705,578and European publication EP-B-0279 863 and PCT Publication WO 97/44371all of which are herein fully incorporated by reference.

Polymer Products

The polymers produced by the process of the invention can be used in awide variety of products and end-use applications. The polymers producedby the process of the invention include linear low density polyethylene,elastomers, plastomers, high density polyethylenes, medium densitypolyethylenes, low density polyethylenes, polypropylene andpolypropylene copolymers.

The polymers, typically ethylene based polymers, have a density in therange of from 0.86 g/cc to 0.97 g/cc, preferably in the range of from0.88 g/cc to 0.965 g/cc, more preferably in the range of from 0.900 g/ccto 0.96 g/cc, even more preferably in the range of from 0.905 g/cc to0.95 g/cc, yet even more preferably in the range from 0.910 g/cc to0.940 g/cc, and most preferably greater than 0.915 g/cc, preferablygreater than 0.920 g/cc, and most preferably greater than 0.925 g/cc.Density is measured in accordance with ASTM-D-1238.

The polymers produced by the process of the invention typically have amolecular weight distribution, a weight average molecular weight tonumber average molecular weight (M_(w)/M_(n)) of greater than 1 to about40, preferably greater than 1.5 to about 15, more preferably greaterthan 2 to about 10, most preferably greater than about 2.0 to about 8.

Also, the polymers of the invention typically have a narrow compositiondistribution as measured by Composition Distribution Breadth Index(CDBI). Further details of determining the CDBI of a copolymer are knownto those skilled in the art. See, for example, PCT Patent Application WO93/03093, published Feb. 18, 1993, which is fully incorporated herein byreference.

The bulky ligand metallocene-type catalyzed polymers of the invention inone embodiment have CDBI's generally in the range of greater than 50% to100%, preferably 99%, preferably in the range of 55% to 85%, and morepreferably 60% to 80%, even more preferably greater than 60%, still evenmore preferably greater than 65%.

In another embodiment, polymers produced using a bulky ligandmetallocene-type catalyst system of the invention have a CDBI less than50%, more preferably less than 40%, and most preferably less than 30%.

The polymers of the present invention in one embodiment have a meltindex (MI) or (I₂) as measured by ASTM-D-1238-E in the range of fromless than 0.01 dg/min to 1000 dg/min, more preferably from about lessthan 0.01 dg/min to about 100 dg/min, even more preferably from about0.1 dg/min to about 50 dg/min, and most preferably from about 0.1 dg/minto about 10 dg/min.

The polymers of the invention in an embodiment have a melt index ratio(I₂₁/I₂) (I₂₁ is measured by ASTM-D-1238-F) of about 5 to less thanabout 2500, preferably about 15 to about 250, more preferably about 10to about 25, more preferably from about 15 to about 25.

The polymers of the invention in a preferred embodiment have a meltindex ratio (I₂₁/I₂) (I₂₁ is measured by ASTM-D-1238-F) of frompreferably greater than 10, more preferably greater than 30, even morepreferably greater that 40, still even more preferably greater than 50and most preferably greater than 65. In an embodiment, the polymer ofthe invention may have a narrow molecular weight distribution and abroad composition distribution or vice-versa, and may be those polymersdescribed in U.S. Pat. No. 5,798,427 incorporated herein by reference.

In yet another embodiment, propylene based polymers are produced in theprocess of the invention. These polymers include atactic polypropylene,isotactic polypropylene, hemi-isotactic and syndiotactic polypropylene.Other propylene polymers include propylene block or impact copolymers.Propylene polymers of these types are well known in the art see forexample U.S. Pat. Nos. 4,794,096, 3,248,455, 4,376,851, 5,036,034 and5,459,117, all of which are herein incorporated by reference.

The polymers of the invention may be blended and/or coextruded with anyother polymer. Non-limiting examples of other polymers include linearlow density polyethylenes produced via conventional Ziegler-Natta and/orbulky ligand metallocene-type type catalysis, elastomers, plastomers,high pressure low density polyethylene, high density polyethylenes,polypropylenes and the like.

Polymers produced by the process of the invention and blends thereof areuseful in such forming operations as film, sheet, and fiber extrusionand co-extrusion as well as blow molding, injection molding and rotarymolding. Films include blown or cast films formed by coextrusion or bylamination useful as shrink film, cling film, stretch film, sealingfilms, oriented films, snack packaging, heavy duty bags, grocery sacks,baked and frozen food packaging, medical packaging, industrial liners,membranes, etc. in food-contact and non-food contact applications.Fibers include melt spinning, solution spinning and melt blown fiberoperations for use in woven or non-woven form to make filters, diaperfabrics, medical garments, geotextiles, etc. Extruded articles includemedical tubing, wire and cable coatings, geomembranes, and pond liners.Molded articles include single and multi-layered constructions in theform of bottles, tanks, large hollow articles, rigid food containers andtoys, etc.

EXAMPLES

In order to provide a better understanding of the present inventionincluding representative advantages thereof, the following examples ofcatalyst compositions of the invention and their polymerization results,are offered.

All polymerizations were performed in a 2.2L Autoclave EngineersZipperclave reactor. The ethylene feed was passed through a 1L Labclearpurification bed and a 1L 3 Å molecular sieve bed. The isobutane diluentwas fed from 5 gallon tanks and passed through a 2.2L Labclearpurification bed. Prepurified hexene was obtained from in-housesuppliers. Pentane and toulene were obtained pre-dried from Aldrich,then degassed and stored over molecular sieves in a drybox. All catalystpreparations were preformed in a nitrogen purged drybox.

Siloxanes were purchased from: Gelest Inc., Tullytown, Pa. Thestructures of

Standard Polymerization Technique

A 2.2 L zipperclave reactor was charged with 1.4 mL of a 25 wt % hexanesolution of tri-n-octylaluminum (TNOA) then with 440 g of isobutane.This mixture was treated with ˜200 psi (1379 kPa) ethylene for 5 to 10minutes then let back down to ˜80 psi (552 kPa). The catalyst wasinjected into the reactor with nitrogen, and the reactor was brought totemperature (60 to 90° C.) with stirring. When the run temperaturestabilized data collection began with ethylene supply to the reactor at125 psi (862 kPa) over solvent pressure. Standard run time was 30minutes. The reactor was vented and flushed with nitrogen then opened tocollect the product.

Exceptions to the normal run profile are noted in the examples. Theaverage run temperature and pressure, and the polymer yield, specificgravity and melt index, for each example, are provided in Table I.

Example 1

A 750 mg portion of a 54 wt % DMS-V31 solution in toluene was treatedwith 45 mg of a 25 wt % TNOA. To this was added cyclopentadienyl(pentamethylcyclopentadienyl) zirconium dimethyl, (10 mg), thenN,N-dimethylanilinium tetra(perfluorophenyl)borate (25 mg). The orangesolution was heated with stirring to ˜60° C. for several minutes thendiluted with 1 ml toluene. The resulting homogeneous orange solution wasadded to 10 ml of pentane. Polymerization of ethylene with 0.3 ml of thedilute solution resulted in a yield of 73 g of polyethylene.

Example 2

A 760 mg portion of a 50 wt % DMS-V31 solution in toluene was treatedwith 45 mg of a 25 wt % TNOA. A toluene (400 mg) solution of(N,N-dimesityl-N′-methyl-ethylenetriamine)ZrMe₂ (10 mg) was added to thesiloxane solution and treated with N,N-dimethylaniliniumtetra(perfluorophenyl)borate (18 mg). The mixture became dark orange andgas was evolved. The reaction was then heated with stirring to ˜60° C.for several minutes then diluted with 10 ml toluene. Polymerization ofethylene with 0.3 ml of the dilute solution resulted in a yield of 3 gof polyethylene.

Example 3

350 mg of DMS-V31, 350 mg of toluene, and 36 mg of a 25 wt % solution inhexane of tri-n-octylaluminum were combined in a vial and mixed for 1 to2 minutes at ˜60° C. A 10 mg portion ofbis(n-propylcyclopentadienyl)HfMe₂ was added with continued stirring andwarning followed by 22 mg of triphenylcarbeniumtetra(perfluorophenyl)borate. The mixture became dark yellow-orange.Stirring and heating continued for several minutes followed by additionof 1 ml toluene. This solution was mixed well then added to 10 mltoluene. Polymerization of ethylene with 0.3 ml of the dilute solutionyielded 11.7 g of polymer.

Example 4

700 mg of a 50 wt % toluene solution of DMS-V31 and 36 mg of a 25 wt %solution in hexane of tri-n-octylaluminum were combined in a vial andmixed for 1 to 2 minutes at ˜60° C. A 10 mg portion ofdimethylsilyl-bis(tetrahydroindenyl)ZrMe₂ was added with continuedstirring and warming followed by 24 mg of triphenylcarbeniumtetra(perfluorophenyl)borate. The mixture became dark yellow-orange.Stirring and heating continued for several minutes followed by additionof 1 ml toluene. This solution was mixed well then added to 10 mltoluene. Polymerization of ethylene with 0.3 ml of the dilute solutionyielded 110 g of polymer.

Example 5

700 mg of a 50 wt % toluene solution of DMS-V31 and 36 mg of a 25 wt %solution in hexane of tri-n-octylaluminum were combined in a vial andmixed for 1 to 2 minutes at ambient temperature. A 10 mg portion ofdimethylsilyl-bis(tetrahydroindenyl)ZrMe₂ was added with continuedstirring followed by 23 mg of triphenylcarbeniumtetra(perfluorophenyl)borate. The mixture became yellow. Stirringcontinued for several minutes followed by addition of 1 ml toluene. Thissolution was mixed well then added to 10 ml toluene. Polymerization ofethylene with 0.3 ml of the dilute solution yielded 100 g of polymer.

Example 6

700 mg of a 50 wt % toluene solution of DES-T23 and 36 mg of a 25 wt %solution in hexane of tri-n-octylaluminum were combined in a vial andmixed for 1 to 2 minutes at ˜60° C. A 10 mg portion of cyclopentadienyl(pentamethylcyclopentadienyl) zirconium dimethyl, was added withcontinued stirring and warming followed by 25 mg ofN,N-dimethylanilinium tetra(perfluorophenyl)borate. The mixture becamedark yellow-orange and gas was evolved. Stirring and heating continuedfor several minutes followed by addition of 1 ml toluene. This solutionwas mixed well then added to 10 ml toluene. Polymerization of ethylenewith 0.3 ml of the dilute solution yielded 63 g of polymer.

Example 7

350 mg of DMS-V52, 350 mg of toluene, and 36 mg of a 25 wt % solution inhexane of tri-n-octylaluminum were combined in a vial and mixed for 1-2minutes at ˜60° C. A 10 mg portion ofdimethylsilyl-bis(tetrahydroindenyl)ZrMe₂ was added with continuedstirring and warming followed by 24 mg of triphenylcarbeniumtetra(perfluorophenyl)borate. The mixture became dark yellow-orange.Stirring and heating continued for several minutes followed by additionof 1 ml toluene. This solution was mixed well then added to 10 mltoluene. Polymerization of ethylene with 0.3 ml of the dilute solutionyielded 19.9 g of polymer.

Example 8

700 mg of a 50 wt % toluene solution of DES-T23 and 36 mg of a 25 wt %solution in hexane of tri-n-octylaluminum were combined in a vial andmixed for 1-2 minutes at ˜60° C. A 10 mg portion ofdimethylsilyl-bis(tetrahydroindenyl)ZrMe₂ was added with continuedstirring and warming followed by 25 mg of triphenylcarbeniumtetra(perfluorophenyl)borate. The mixture became dark yellow. Stirringand heating continued for several minutes followed by addition of 1 mltoluene. This solution was mixed well then added to 10 ml toluene.Polymerization of ethylene with 0.3 ml of the dilute solution yielded 60g of polymer.

Example 9

700 mg of a 50 wt % toluene solution of DMS-V31 was combined with a 10mg portion of dimethylsilyl-bis(tetrahydroindenyl)ZrMe₂in a vial andmixed for 1-2 minutes at ˜60° C., followed by 25 mg oftriphenylcarbenium tetra(perfluorophenyl)borate. The mixture became darkyellow. Stirring and heating continued for several minutes followed byaddition of 1 ml toluene. This solution was mixed well then added to 10ml toluene. Polymerization of ethylene with 0.3 ml of the dilutesolution yielded 17.4 g of polymer.

Example 10

700 mg of a 50 wt % toluene solution of DMS-V31 and 36 mg of a 25 wt %solution in hexane of tri-n-octylaluminum were combined in a vial andmixed for 1-2 minutes at ˜60° C. A 10 mg portion ofdimethylsilyl-bis(tetrahydroindenyl)ZrMe₂ was added with continuedstirring and warming followed by 13 mg of tris(perfluorophenyl)borane.Stirring and heating continued for several minutes followed by additionof 1 ml toluene. This solution was mixed well then added to 10 mltoluene. Polymerization of ethylene with 0.3 ml of the dilute solutionyielded 30 g of polymer.

Example 11

700 mg of a 50 wt % toluene solution of DMS-V31 and 36 mg of a 25 wt %solution in hexane of tri-n-octylaluminum were combined in a vial andmixed for 1-2 minutes at ˜60° C. A 10 mg portion ofdimethylsilyl-bis(tetrahydroindenyl)ZrMe₂ was added with continuedstirring and warming followed by 25 mg of triphenylcarbeniumtetra(perfluorophenyl)borate. The mixture became dark yellow. Stirringand heating continued for several minutes followed by addition of 1 mltoluene. This solution was mixed well then added to 10 ml pentane.Polymerization of ethylene with 0.3 ml of the dilute solution yielded 15g of polymer.

Example 12

175 mg of a 50 wt % toluene solution of DMS-V31 and 36 mg of a 25 wt %solution in hexane of tri-n-octylaluminum were combined in a vial andmixed for 1-2 minutes at ˜60° C. A 0.2 ml portion of a 0.125M toluenesolution of [1-(2-pyridyl) N-1-methylethyl][1-N-2,6diisopropylphenylamido] zirconium tribenzyl was added with continuedstirring and warming followed by 23 mg of triphenylcarbeniumtetra(perfluorophenyl)borate. Stirring and heating continued for severalminutes followed by addition of 1 ml toluene. This solution was mixedwell then added to 10 ml toluene. Polymerization of ethylene with 0.3 mlof the dilute solution yielded 18.8 g of polymer.

Example 13

175 mg of a 50 wt % toluene solution of DMS-V31 and 36 mg of a 25 wt %solution in hexane of tri-n-octylaluminum were combined in a vial andmixed for 1-2 minutes at ˜60° C. A 0.3 ml portion of a 0.08M toluenesolution of [1-(2-pyridyl) N-1-methylethyl] [1-N-2,6diisopropylphenylamido] [2-methyl-1-phenyl-2-propoxy] zirconium dibenzylwas added with continued stirring and warming followed by 23 mg oftriphenylcarbenium tetra(perfluorophenyl)borate. Stirring and heatingcontinued for several minutes followed by addition of 1 ml toluene. Thissolution was mixed well then added to 10 ml toluene. Co-polymerizationof ethylene with hexene, with 0.3 ml of the dilute solution, yielded16.9 g of polymer.

Example 14

A 350 mg portion of a 50 wt % DMS-V31 in toluene was treated with 36 mgof 25 wt % tri-n-octylaluminum in hexanes. A toluene (0.5 ml) solutionof 12 mg of (N,N-dimesityl-N′-methyl-ethylenetriamine)ZrMe₂ was added tothe siloxane and treated with 23 mg of triphenylcarbeniumtetra(perfluorophenyl)borate. The mixture became dark orange. Thereaction was then stirred for several minutes then 0.5 ml of toluene wasadded. The solution was mixed further and then added to 10 ml toluene.Polymerization of ethylene with 0.3 ml of the dilute solution resultedin a yield of 16.3 g of polyethylene.

Example 15

A 700 mg portion of a 54 wt % DMS-V31 solution in toluene was treatedwith 72 mg of a 25 wt % TNOA. cyclopentadienyl(pentamethylcyclopentadienyl) zirconium dichloride (10 mg), was addedand the mixture was warmed to ˜60° C. until the metallocene dissolved.At this point the solution was bright yellow. The metallocene wasactivated with 23 mg of triphenylcarbenium tetra(perfluorophenyl)borate.The orange solution was heated with stirring to 60° C. for severalminutes then diluted with 1 ml toluene. The resulting solution wasstirred with warming for several minutes with 1 ml toluene and mixedfurther. This solution was then added to 10 ml toluene. Polymerizationof ethylene with 0.3 ml of the dilute solution resulted in a yield of 10g of polyethylene.

Example 16

A 700 mg portion of a 54 wt % FMV-4031 in toluene was treated with 73 mgof 25 wt % tri-n-octylaluminum in hexanes. Thepentamethylcyclopentadienyl (n-propyl-cyclopentadienyl) zirconiumdichloride (Cp*Cp^(n−pr)ZrCl₂) (11 mg), was added to the siloxane andmixed for several minutes. The solution was then treated with 23 mg oftriphenylcarbenium tetra(perfluorophenyl)borate. The reaction wasstirred for several minutes, then 1 ml of toluene was added. Thesolution was mixed further and then added to 10 ml toluene.Polymerization of ethylene with 0.3 ml of the dilute solution resultedin a yield of 29.4 g of polyethylene.

Example 17

A 350 mg portion of a 54 wt % FMV-4031 in toluene was treated with 72 mgof 25 wt % tri-n-octylaluminum in hexanes.Dimethylsilyl-bis(tetrahydroindenyl)ZrMe₂ (11 mg) was added to thesiloxane and mixed for several minutes. The solution was then treatedwith 23 mg of triphenylcarbenium tetra(perfluorophenyl)borate. Thereaction was stirred for several minutes, then 1 ml of toluene wasadded. The solution was mixed further and then added to 10 ml toluene.Polymerization of ethylene with 0.3 ml of the dilute solution resultedin a yield of 33 g of polyethylene.

Example 18

A 700 mg portion of a 50 wt % DMS-V31 in toluene was treated with 36 mgof 25 wt % tri-n-octylaluminum in hexanes. A toluene (0.5 ml) solutionof 9 mg of (N,N-dimesityl-N′-methyl-ethylenetriamine)ZrMe₂ was added tothe siloxane followed by a 4.5 mg portion ofdimethylsilyl-bis(tetrahydroindenyl)ZrMe₂. The mixture was then treatedwith 24 mg of triphenylcarbenium tetra(perfluorophenyl)borate. Thereaction was then stirred for several minutes then 0.5 ml of toluene wasadded. The solution was mixed further and then added to 10 ml toluene.Polymerization of ethylene with 0.3 ml of the dilute solution resultedin a yield of 76.5 g of polyethylene.

Example 19

A 11.9 g sample of silica dried at elevated temperatures was mixed intoluene with 6.5 g of a 25 wt % hexanes solution of triethylaluminum(TEAL) for 15 minutes. The silica was recovered by filtration and driedin vacuuo. A 700 mg portion of a 50 wt % DES-T23 in toluene was treatedwith 46 mg of 25 wt % tri-n-octylaluminum in hexanes. cyclopentadienyl(pentamethylcyclopentadienyl) zirconium dimethyl (10 mg), was added tothe siloxane followed by 24 mg of triphenylcarbeniumtetra(perfluorophenyl)borate. The reaction was stirred for severalminutes then 1.4 ml of toluene was added. The solution was mixed furtherand then 0.5 g of the TEAL-treated silica was added and the mixture wasstirred with a spatula. The solids were then dried in vacuuo.Polymerization of ethylene with 0.1 g of the finished solid resulted ina yield of 38.8 g of polyethylene. Note that the pretreatment ofisobutane diluent with ethylene as described in the generalpolymerization technique was not performed in this example.

Example 20

500 mg of FMV-4031 and 111 mg of a 25 wt % solution in hexane oftri-n-octylaluminum were combined in a vial and mixed. A 32 mg portionof bis(n-propylcyclopentadienyl)HfMe₂ was added with continued stirringfollowed by 70 mg of triphenylcarbenium tetra(perfluorophenyl)borate.Stirring continued for several minutes followed by addition of 1 mltoluene. To this mixture was added silica (1 g) previously treated witha mixture of MAO and bis(n-propylcyclopentadienyl)ZrCl₂. The resultingsolids were mixed with a spatula and dried in vacuuo. Polymerization ofethylene with 0.1 g of the finished solids yielded 64.8 g of polymer.Note that the pretreatment of isobutane diluent with ethylene asdescribed in the general polymerization technique was not performed inthis example.

Example 21

700 mg of FMV-4031 and 36 mg of a 25 wt % solution in hexane oftri-n-octylaluminum were combined in a vial and mixed. A 15 mg portionof (N,N′-2,6-diisopropylphenyl-ethylene-di-imine)NiBr₂ was added, atwhich point the solution became dark violet. After a few minutes ofmixing, 23 mg of triphenylcarbenium tetra(perfluorophenyl)borate wasadded. Stirring continued for several minutes followed by addition of 1ml toluene. The solution was mixed then added to 10 ml of toluene.Polymerization of ethylene with 0.3 ml of the dilute solution yielded0.50 g of polymer.

TABLE I Example Average Run Average Run Polymer Yield Specific ActivityFlow Index Number Temp. ° C. Pressure psi (kPa) g g/mmol · atm · h I₂₁(dg/min) 1 90 378 (2606) 73.0 25514 4.0 2 90 393 (2710) 3.0 933 0.2 3 90379 (2613) 11.7 4149 NF* 4 90 375 (2586) 110 38547 2.2 5 90 373 (2572)100 36323 — 6 90 376 (2592) 63.0 22526 3.5 7 90 381 (2627) 19.9 6749 5.58 90 376 (2592) 60.8 22925 5.0 9 90 376 (2592) 17.4 6120 4.0 10 90 376(2592) 30.6 10814 5.2 11 90 377 (2599) 15.6 5470 3.6 12 90 377 (2599)18.8 6584 0.6 13 90 376 (2592) 16.9 6001 2.6 14 61 376 (2592) 16.3 5691NF* 15 90 375 (2586) 10.0 3546 13 16 90 401 (2765) 29.4 8595 0.5 17 90377 (2599) 33.1 11633 1.4 18 90 374 (2579) 76.5 27508 3.1 19 90 378(2606) 38.8 4636 4.5 20 90 378 (2606) 64.8 1675 2.4 21 61 380 (2620)0.50 100 — *NF indicates the polymer does not flow under test conditions

While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to variations notnecessarily illustrated herein. For example, more than one siloxane maybe utilized to solubilize or emulsify more than one polymerizationcatalyst compound and/or more than one activator compound. For thisreason, then, reference should be made solely to the appended claims forpurposes of determining the true scope of the present invention.

I claim:
 1. A process of polymerizing olefin(s) in the presence of acatalyst system; the catalyst system prepared by combining an oil oramorphous solid with a metallocene catalyst compound or Group 15 metalcontaining polymerisation catalyst compound; wherein the oil oramorphous solid is represented by the following formulae:T-M(R¹)₂—O-(M(R²)₂—O)_(n-)-M(R¹)₂-T orT-M(R¹)₂—O-(M(R²)₂—O)_(n)-(M(R³)₂—O)_(m)-M(R¹)₂-T wherein each of T, R¹,R², and R³ are independently selected from the group consisting ofhydride, alkyl, alkoxy, aryl, substituted aryl, cycloalkyl, substitutedcyclic alkyl, cyclic arylalkyl, substituted cyclic arylalkyl, vinyl,silyl, silyloxy, vinylsiloxy, haloaryl, haloalkyl, and vinylsilylcontaining group, wherein at least one T is a vinyl-containing group;each M is independently an atom of Group 14 of the Periodic Table; O isoxygen; and wherein n and m independently an integer between about 1 and40,000.
 2. The process of claim 1, wherein each T is independently amethyl, ethyl or vinyl group.
 3. The process of claim 1, wherein each R¹and R² is independently a methyl or ethyl group.
 4. The process of claim1, wherein in each R³ is independently a halogenated or non-halogenatedmethyl, ethyl, propyl or phenyl group.
 5. The process of claim 1,wherein the oil or amorphous solid comprises a siloxane oil orcombination of siloxano oils having a viscosity of between about 100 cStand about 500,000 cSt and a number average molecular weight betweenabout 60 and about 100,000.
 6. The process of claim 1, wherein thecatalyst system further comprises a stoichiometric activator; whereinthe stoichiometric activator is represented by the formula: (L-H)_(d)⁺(A^(d−)) wherein L is an neutral Lewis base; H is hydrogen; (L-H)⁺is aBronsted acid; A^(d−) is a non-coordinating anion having the charge d−;and d is an integer from 1 to
 3. 7. The process of claim 1, wherein thecatalyst system comprises a solution or emulsion.
 8. The process ofclaim 1, wherein the catalyst system is combined with one or moresupports or carriers.
 9. The process of claim 8, wherein the support isan inorganic oxide.
 10. The process of claim 6, wherein thestoichiometric activator is selected from tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tris(perfluorophenyl)borane,tris(perfluoronaphthyl)borane, polyhalogenated heteroborane anions andmixtures thereof.
 11. The process of claim 1, wherein the process is aslurry or gas phase process.
 12. The process of claim 11, wherein theprocess takes place at a temperature of from 50 to 200° C.
 13. Theprocess of claim 1, wherein the olefins are selected from ethylene andat least one alpha-olefin having from 4 to 12 carbon atoms.
 14. Theprocess of claim 1, wherein the process is a fluidized bed gas phaseprocess at a temperature of from 60° C. to 115° C.
 15. The process ofclaim 1, wherein the oil or amorphous solid, polymerization catalyst andoptionally an activator, are combined and heated to between about 30° C.and about 250° C.
 16. The process of claim 15, wherein the oil oramorphous solid and polymerization catalyst, and optionally anactivator, are combined and heated to between about 40° C. and about100° C.
 17. The process of claim 1, wherein the weight ratio of oil oramorphous solid-to-weight polymerization catalyst is between about 1:10to 100:1.
 18. The process of claim 1, wherein the weight ratio of oil oramorphous solid-to-weight polymerization catalyst is between 1:1 andabout 70:1.
 19. The process of claim 1, wherein a support or carrier isabsent from the catalyst system as used in a polymerization process.